RESUMO
Methane conversion to valuable chemicals is a highly challenging and desirable reaction. Photocatalysis is a clean pathway to drive this chemical reaction, avoiding the high temperature and pressure of the syngas process. Titanium dioxide, being the most used photocatalyst, presents challenges in controlling the oxidation process, which is believed to depend on the metal sites on its surface that function as heterojunctions. Herein, we supported different metals on TiO2 and evaluated their activity in methane photooxidation reactions. We showed that Ni-TiO2 is the best photocatalyst for selective methane conversion, producing impressively high amounts of methanol (1.600 µmol·g-1) using H2O2 as an oxidant, with minimal CO2 evolution. This performance is attributed to the high efficiency of nickel species to produce hydroxyl radicals and enhance H2O2 utilization as well as to induce carrier traps (Ti3+ and SETOVs sites) on TiO2, which are crucial for C-H activation. This study sheds light on the role of catalyst structure in the proper control of CH4 photoconversion.
RESUMO
In this work, the prepared cobalt oxide decorated boron-doped g-C3N4 (CoOx/g-C3N4) heterojunction exhibits remarkable activity in CO2 reduction (CO2RR), resulting in high yields of CH3COOH (â¼383 µmol·gcatalyst-1) and CH3OH (â¼371 µmol·gcatalyst-1) with 58% selectivity to C2+ under visible light. However, the same system leads to high H2 evolution (HER) by increasing the cobalt oxide content, suggesting that the selectivity and preference for the CO2RR or HER depend on oxide decoration. By comparing HER and CO2RR evolution in the same system, this work provides critical insights into the catalytic mechanism, indicating that the CoOx/g-C3N4 heterojunction formation is necessary to foster high visible light photoactivity.